JP3882256B2 - Recording liquid, ink jet recording method, and dye for recording liquid - Google Patents

Description

【０００８】
［式中、Ａ¹ 、Ａ² は−ＳＯ₃ Ｈ基で置換されていても良いフェニル基、又はナフチル基を表わし、Ｒ¹ 、Ｒ² 、Ｒ³ 及びＲ⁴ は各々独立に、水素原子、置換もしくは非置換の炭素数１〜４のアルキル基、置換もしくは非置換の炭素数１〜４のアルコキシ基、−ＮＨＣＯＲ⁵ 基（但し、Ｒ⁵ は−ＮＨ₂ 又は炭素数１〜４のアルキル基を表わす。）、ハロゲン原子、および−ＣＮ基から選ばれる基を表わし、Ｘ¹ 及びＸ² は夫々独立に−ＮＲ⁶ Ｒ⁷ 基又は−ＯＲ⁸ 基（但し、Ｒ⁶ 、Ｒ⁷ 及びＲ⁸ は、各々独立に水素原子、炭素数１〜８のアルキル基、炭素数１〜３のアルケニル基、アリール基、アラルキル基、シクロヘキシル基、または含窒素複素環基を表わし、これらのうち水素原子以外は置換基を有していてもよく、また、Ｒ⁶ 及びＲ⁷ は結合される窒素原子と共に５〜６員環を形成していてもよい。）を表わし、
Ｙ¹ は下記一般式（III)〜（VII)のいずれか１つで示される二価の結合基を示す。］
【０００９】
【化９】

【００１０】
（式中、Ｂ¹ 及びＢ² は各々独立に下記の一般式（II−ａ）又は（II−ｂ）
【００１１】
【化１０】

【００１２】
（式（II−ａ）中、Ｒ¹⁶は炭素数１〜４のアルキル基を表わし、Ｒ¹⁷は水素原子、−ＣＮ基、−ＣＯＮＨ₂ 基、又は−ＣＯＯＨ基を表わし、Ｒ¹⁸は水素原子、あるいは、置換又は未置換の炭素数１〜４のアルキル基を表わす。）
【００１３】
【化１１】

【００１４】
（式（II−ｂ）中、Ｒ¹⁹は水素原子、メチル基又は−ＣＯＯＨ基を表わし、Ｒ²⁰、Ｒ²¹及びＲ²²は各々独立に水素原子、−ＳＯ₃ Ｈ基、塩素原子又はメチル基を表わす。）
で示される基を表わし、Ｒ⁹ 、Ｒ¹⁰、Ｒ¹¹及びＲ¹²は各々独立に水素原子、−ＳＯ₃ Ｈ基又は−ＣＯＯＨ基を表わし、Ｘ³ 及びＸ⁴ は各々独立に−ＮＲ¹³Ｒ¹⁴基又は−ＯＲ¹⁵基、
（但し、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵は、それぞれ水素原子、炭素数１〜８のアルキル基、炭素数１〜３のアルケニル基、アリール基、アラルキル基、シクロヘキシル基、または含窒素複素環基を表わし、これらのうち水素原子以外は置換基を有していてもよく、また、Ｒ¹³及びＲ¹⁴は結合される窒素原子と共に５〜６員環を形成していてもよい。）を表わし、
Ｙ² は下記一般式（III)〜（VII)のいずれか１つで示される二価の結合基を示し、ｎは０または１を表わす。］
【００１５】
【化１２】

【００１６】
（式（III)中、ａ及びｂはそれぞれ０〜６の数を表わし、ｃは０又は１を表わす。）
【００１７】
【化１３】

【００１８】
（式（IV）中、Ｖ，Ｗはそれぞれ水素原子、又は、炭素数１〜４のアルキル基を表わす。）
【００１９】
【化１４】

【００２０】
【発明の実施の形態】
以下本発明を詳細に説明する。
本発明で使用される色素は、遊離酸の形が前記一般式（Ｉ）で示される色素及び一般式（II）で表される色素から選ばれるものである。
前記一般式（Ｉ）において、Ａ¹ 及びＡ² で表わされる基としては、フェニル基又は２−ナフチル基が好ましく、それぞれ少なくとも１つの−ＳＯ₃ Ｈ基で置換されていることがより好ましい。
【００２１】
Ｒ¹ 、Ｒ² 、Ｒ³ 及びＲ⁴ で表わされる置換基としては、各々独立に、水素原子、置換もしくは非置換の炭素数１〜４のアルキル基（例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、トリフロロメチル基等）、置換もしくは非置換の炭素数１〜４のアルコキシ基（例えば、メトキシ基、エトキシ基、イソプロポキシ基、ｎ−ブトキシ基等）、−ＮＨＣＯＲ⁵ 基（例えば、−ＮＨＣＯＮＨ₂ 基、−ＮＨＣＯＣＨ₃ 基、−ＮＨＣＯＣ₃ Ｈ₇ （ｉ）等）、ハロゲン原子（例えば、フッ素原子、塩素原子等）及び−ＣＮ基から選ばれる基を表わす。
【００２２】
Ｘ¹ 及びＸ² は夫々独立に−ＮＲ⁶ Ｒ⁷ 基又は−ＯＲ⁸ 基を表わし、Ｒ⁶ 、Ｒ⁷ 及びＲ⁸ としては、それぞれ独立に、水素原子、置換もしくは非置換の炭素数１〜８のアルキル基（例えば、メチル基、カルボキシメチル基、エチル基、ｎ−ブチル基、ｎ−オクチル基、ヒドロキシエチル基、イソプロピル基、ｔｅｒｔ−ブチル基等）、置換もしくは非置換の炭素数１〜３のアルケニル基（例えば、ビニル基、アリル基等）、置換もしくは非置換の炭素数６〜２０のアリール基（例えば、フェニル基、４−ニトロフェニル基、４−ブチルフェニル基、４−カルボキシフェニル基等）、置換もしくは非置換の炭素数７〜２０のアラルキル基（例えば、ベンジル基、フェネチル基等）、置換もしくは非置換のシクロヘキシル基、又は置換もしくは非置換の５〜６員の含窒素複素環基（例えば、ピリジル基等）等が挙げられる。また、Ｒ⁶ 及びＲ⁷ は結合される窒素原子と共に５員環または６員環を形成していてもよく、具体的には−ＮＲ⁶ Ｒ⁷ として、ピロリジノ基、ピペリジノ基、３，５−ジメチルピペリジノ基、モルホリノ基、４−メチルピペラジニル基等が挙げられる。
【００２３】
前記式（Ｉ）で示される色素は、分子全体として−ＳＯ₃ Ｈ基を２個〜８個有していることが好ましく、２個〜６個有していることがより好ましい。
また、前記式（Ｉ）で示される色素の中でも、遊離酸の形が下記の式（VIII）で示されるような、連結基Ｙ¹ を介して左右対称の構造の色素が好ましく使用される。この色素は、色調、耐水性、実用性の面で好ましい。
【００２４】
【化１５】

【００２５】
（式中、Ａ¹ 、Ｒ¹ 、Ｒ² 、Ｘ¹ 及びＹ¹ は前記式（Ｉ）と同義である）
前記式（II）において、Ｂ¹ 及びＢ² は各々独立に式（II−ａ）又は（II−ｂ）を表わし、式（II−ａ）において、Ｒ¹⁶は炭素数１〜４のアルキル基（例えばメチル基等）を表わし、Ｒ¹⁷は水素原子、−ＣＮ基、−ＣＯＮＨ₂ 基、−ＣＯＯＨ基を表わし、Ｒ¹⁸は水素原子、置換あるいは未置換の炭素数１〜４のアルキル基（例えばメチル基、イソプロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ヒドロキシエチル基等）を表わす。
【００２６】
Ｒ¹³、Ｒ¹⁴及びＲ¹⁵としては、それぞれ独立に、水素原子、置換もしくは非置換の炭素数１〜８のアルキル基（例えば、メチル基、カルボキシメチル基、エチル基、ｎ−ブチル基、ｎ−オクチル基、ヒドロキシエチル基、イソプロピル基、ｔｅｒｔ−ブチル基等のアルキル基）、置換もしくは非置換の炭素数１〜３のアルケニル基（例えば、ビニル基、アリル基等）、置換もしくは非置換の炭素数６〜２０のアリール基（例えば、フェニル基、４−ニトロフェニル基、３−スルホフェニル基、４−ブチルフェニル基、４−カルボキシフェニル基等）、置換もしくは非置換の炭素数７〜２０のアラルキル基（例えば、ベンジル基、フェネチル基等）、置換もしくは非置換のシクロヘキシル基又は置換もしくは非置換の５〜６員の含窒素複素環基（例えば、ピリジル基等）等が挙げられる。
【００２７】
Ｒ¹³及びＲ¹⁴は結合される窒素原子と共に５員環または６員環を形成していてもよく、具体的には−ＮＲ¹³Ｒ¹⁴としてピロリジノ基、ピペリジノ基、３，５−ジメチルピペリジノ基、モルホリノ基、４−メチル−ピペラジニル基等が挙げられる。
前記一般式（II）で示される色素は、分子全体として−ＳＯ₃ Ｈ基を２〜８個有していることが好ましく、２〜６個がより好ましい。
【００２８】
本発明で使用される色素は、前記一般式（Ｉ）又は（II）で示される遊離酸型のまま使用してもよいが、製造時塩型で得られた場合はそのまま使用してもよいし、所望の塩型に変換してもよい。また酸基の一部が塩型のものであってもよく、塩型の色素と遊離酸型の色素が混在していてもよい。このような塩型の例としてはＮａ，Ｌｉ，Ｋ等のアルカリ金属の塩、アルキル基、ヒドロキシアルキル基で置換されていてもよいアンモニウムの塩、有機アミンの塩があげられる。有機アミンの例としては、低級アルキルアミン、ヒドロキシ置換低級アルキルアミン、カルボキシ置換低級アルキルアミン及び炭素数２〜４のアルキレンイミン単位を２〜１０個有するポリアミン等があげられる。これらの塩型の場合、その種類は１種類に限られず複数種混在していてもよい。
【００２９】
また、本発明で使用する色素の構造において、その１分子中に酸基が複数個含まれる場合は、その複数の酸基は塩型あるいは酸型であり、互いに異なるものであってもよい。
これ等の色素の具体例としては、例えば以下のＩ−（１）〜Ｉ−（１０）及びII−（１）〜II−（２０）に示す構造の色素が挙げられる。
【００３０】
【化１６】

【００３１】
【化１７】

【００３２】
【化１８】

【００３３】
【化１９】

【００３４】
【化２０】

【００３５】
【化２１】

【００３６】
【化２２】

【００３７】
【化２３】

【００３８】
【化２４】

【００３９】
【化２５】

【００４０】
一般式（Ｉ）又は（II）で示される色素は、それ自体周知の方法に従って製造することができる。
例えば前記Ｉ−（１）で示される色素は（Ａ）〜（Ｂ）の工程で製造できる。（Ａ）３−アミノ−１，５−ナフタレンジスルホン酸（Ｃ酸）とｍ−トルイジンとから常法［例えば細田豊著「新染料化学」（昭和４８年１２月２１日技報堂発行）第３９６〜４０９頁参照］に従って、ジアゾ化カップリング工程を経てモノアゾ化合物を製造する。
【００４１】
（Ｂ）得られたモノアゾ化合物を塩化シアヌル懸濁液にｐＨ４〜６、温度０〜５℃を保持しながら加えて数時間反応を行う。次いで室温にて弱アルカリ性で１，４−ビスアミノプロピルピペラジンをモノアゾ化合物に対して０．５モル比加えて数時間縮合反応を行う。
【００４２】
次いで２５％水酸化ナトリウム水溶液を５０〜６０℃に加え、加水分解反応を行った後、冷却して、塩化ナトリウムで塩析することにより、目的の染料を得る。
記録液中における前記一般式（Ｉ）の色素あるいは前記一般式（II）の色素の含有量としては、合計で記録液全量に対して０．５〜５重量％、特に２〜４重量％程度が好ましい。
【００４３】
本発明の記録液に用いられる水性媒体としては、水及び水溶性有機溶剤が用いられ、水溶性有機溶剤としては、例えばエチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール（分子量１９０〜４００）、グリセリン、Ｎ−メチルピロリドン、Ｎ−エチルピロリドン、１，３−ジメチルイミダゾリジノン、チオジエタノール、ジメチルスルホキシド、エチレングリコールモノアリルエーテル、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、２−ピロリドン、スルホラン、エチルアルコール、イソプロパノール等を含有しているのが好ましい。これ等の水溶性有機溶剤は、通常記録液の全量中の１〜５０重量％の量で使用される。一方、水は記録液の全量中の４５〜９５重量％の量使用される。
【００４４】
本発明の記録液に、その全量中、０．１〜１０重量％、好ましくは０．５〜５重量％の尿素、チオ尿素、ビウレット、セミカルバジドから選ばれる化合物を含有させたり、又０．００１〜５．０重量％の界面活性剤を含有させたりすることによって、印字後の速乾性及び印字品位をより一層改良することができる。
【００４５】
【実施例】
以下、本発明を実施例について更に詳細に説明するが、本発明はその要旨を越えない限りこれ等の実施例に限定されるものではない。
【００４６】
［実施例１］
ジエチレングリコール１０重量部、イソプロピルアルコール３重量部、前記Ｉ−（１）の色素３重量部に水を加え、アンモニア水でｐＨを９に調整して全量を１００重量部とした。
この組成物を充分に混合して溶解し、孔径１μｍのテフロンフィルターで加圧濾過した後、真空ポンプ及び超音波洗浄機で脱気処理して記録液を調製した。
【００４７】
得られた記録液を使用し、インクジェットプリンター（商品名ＨＧ−３０００、エプソン社製品）を用いて電子写真用紙にインクジェット記録を行い、鮮明な色調のイエロー色印字物を得た。また下記に（ａ），（ｂ）及び（ｃ）の方法による諸評価を行った結果を示す。
【００４８】
（ａ）記録画像の耐光性：
キセノンフェードメーター（スガ試験機社製品）を用い、記録紙に１００時間照射したが、照射後の変退色は小さかった。
（ｂ）記録画像の耐水性：
（１）試験方法
水道水中に記録画像を５分間浸漬したのち、
▲１▼目視にて画像の滲みを調べた。
▲２▼浸漬前後のベタ印字部分のＯＤ値をマクベス濃度計（ＴＲ９２７）にて測定した。
【００４９】
（２）試験結果
上記▲１▼の結果画像のにじみはわずかであった。
また上記▲２▼の浸漬前後のベタ印字部分の濃度変化を下記式によるＯＤ残存率で示すと、９４．２％であった。
（ｃ）記録液の保存安定性：
記録液をテフロン容器に密閉し、５℃及び６０℃で１ケ月間保存した後の変化を調べたところ、不溶物の析出は認められなかった。
【００５０】
【数１】

【００５１】
［実施例２］
グリセリン５重量部、エチレングリコール１０重量部、前記II−（１）の色素２．５重量部に水を加え、水酸化リチウム水溶液でｐＨを９に調整して全量を１００重量部とし、この組成物を実施例１に記載の方法により処理して記録液を調製した。この記録液を用いて、実施例１と同様に印字を行った結果、鮮明な色調のイエロー色記録物を得た。またこの記録物に対し、実施例１の（ａ）〜（ｃ）による諸評価を行った。その結果、実施例１と同様に何れも良好な結果が得られた。
またＯＤ残存率は８４．５％であった。
【００５２】
［実施例３］
ジエチレングリコール１０重量部、Ｎ−メチルピロリドン５重量部、イソプロピルアルコール３重量部、前記II−（１６）の色素３重量部に水を加え、アンモニア水でｐＨを９に調整して全量を１００重量部とし、この組成物を実施例１に記載の方法により処理して記録液を調製した。この記録液を用いて、実施例１と同様に印字を行った結果、鮮明な色調のイエロー色記録物を得た。またこの記録物に対し、実施例１の（ａ）〜（ｃ）による諸評価を行った。その結果、実施例１と同様に何れも良好な結果が得られた。
またＯＤ残存率は８６．３％であった。
【００５３】
［実施例４〜２７］
実施例１において用いた前記Ｉ−（１）の色素の代わりに、前記Ｉ−（２）〜Ｉ−（１０），II−（２）〜II−（１５），II−（１７）〜II−（２０）の色素をそれぞれ使用した以外は、実施例１の方法により記録液を調製し、印字を行い、この記録物に対して実施例１の（ａ）〜（ｃ）による諸評価を行った。その結果、実施例１と同様に何れも良好な結果を得た。
またＩ−（２）の色素を用いた場合のＯＤ残存率は８６．１％であり、Ｉ−（３）の色素を用いた場合は８０．２％であった。
【００５４】
【発明の効果】
本発明の記録液は、インクジェット記録用、筆記用具用として用いられ、普通紙に記録した場合、鮮明なイエロー色系の記録物を得ることができ、その印字濃度、耐光性及び耐水性が優れている他、記録液としての保存安定性も良好である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a recording liquid. Specifically, the present invention relates to a recording liquid suitable for ink jet recording.
[0002]
[Prior art]
A so-called ink jet recording method has been put to practical use in which recording is performed by ejecting droplets of a recording liquid containing a water-soluble dye such as a direct dye or an acid dye from a minute ejection orifice.
This recording solution is fast to fix on general-purpose office paper such as PPC (plain paper copier) and fan hold paper (continuous paper for computers, etc.) for electrophotographic paper, and the print quality of printed matter. In other words, it is required to have good printing characteristics, i.e., no blurring and clear outline, and excellent stability when stored as a recording liquid. Limited.
[0003]
On the other hand, the dye for the recording liquid has sufficient solubility in the limited solvent as described above, and is stable when stored as a recording liquid for a long period of time. However, it is difficult to satisfy many of these requirements at the same time.
For this reason, various methods (for example, JP 59-8775, JP 59-226072, JP 60-94477, JP 61-2771, JP 61-101572, JP 4-233975, JP 7-126560 and JP-A-7-316446) have been proposed, but have not yet fully satisfied market demands.
[0004]
[Problems to be solved by the invention]
The present invention has good print quality even when recorded on plain paper, such as for inkjet recording and writing utensils, etc., and has a high density of recorded images, excellent light resistance and water resistance, and color tone of recorded images. Therefore, it is an object of the present invention to provide a yellow recording liquid having good stability when stored for a long time.
[0005]
In particular, yellow dyes conventionally used in recording liquids have good water resistance, and since the recording material is mainly pulp paper, commercial dyes having high affinity for cellulose, that is, high directity ( For example, sulfur dyes, azoic dyes, etc.) are unclear in color tone, and conversely, acid dyes with clear color tone are inferior in water resistance, so the development of yellow pigments that satisfy both color tone and water resistance has been desired. .
[0006]
[Means for Solving the Problems]
The present inventors have obtained a recording liquid having a comprehensively balanced performance when using a specific dye as a recording liquid component, in particular, having both color tone and water resistance balanced, The present invention has been achieved by confirming that the object has been achieved. That is, the gist of the present invention is that the free acid form contains at least one dye selected from the dye represented by the following general formula (I) and the dye represented by the following general formula (II) and an aqueous medium. It exists in the characteristic recording liquid.
[0007]
[Chemical 8]

[0008]
[Wherein, A ¹ and A ² represent a phenyl group which may be substituted with a —SO ₃ H group or a naphthyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, —NHCOR ⁵ group (where R ⁵ is —NH ₂ or an alkyl group having 1 to 4 carbon atoms) Represents a group selected from a halogen atom and a —CN group, and X ¹ and X ² are each independently an —NR ⁶ R ⁷ group or an —OR ⁸ group (provided that R ⁶ , R ⁷ and R ⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group, and of these, other than a hydrogen atom May have a substituent, and R ⁶ and R ⁷ are bonded to each other. And may form a 5- to 6-membered ring together with the nitrogen atom),
Y ¹ represents a divalent linking group represented by any ^one of the following general formulas (III) to (VII). ]
[0009]
[Chemical 9]

[0010]
(In the formula, B ¹ and B ² are each independently represented by the following general formula (II-a) or (II-b):
[0011]
[Chemical Formula 10]

[0012]
(In the formula (II-a), R ¹⁶ represents an alkyl group having 1 to 4 carbon atoms, R ¹⁷ represents a hydrogen atom, —CN group, —CONH ₂ group, or —COOH group, and R ¹⁸ represents a hydrogen atom. Or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.)
[0013]
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[0014]
(In the formula (II-b), R ¹⁹ represents a hydrogen atom, a methyl group or a —COOH group, and R ²⁰ , R ²¹ and R ²² each independently represents a hydrogen atom, a —SO ₃ H group, a chlorine atom or a methyl group. Represents.)
R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom, —SO ₃ H group or —COOH group, and X ³ and X ⁴ each independently represent —NR ¹³ R ¹⁴ groups or -OR ¹⁵ groups,
(However, R < ¹³ >, R <^14> and R < ¹⁵ > are respectively a hydrogen atom, a C1-C8 alkyl group, a C1-C3 alkenyl group, an aryl group, an aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group. And a hydrogen atom other than a hydrogen atom may have a substituent, and R ¹³ and R ¹⁴ may form a 5- or 6-membered ring together with a nitrogen atom to be bonded. ,
Y ² represents a divalent linking group represented by any one of the following general formulas (III) to (VII), and n represents 0 or 1. ]
[0015]
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[0016]
(In formula (III), a and b each represents a number of 0 to 6, and c represents 0 or 1)
[0017]
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[0018]
(In formula (IV), V and W each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
[0019]
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[0020]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The dye used in the present invention is one in which the form of the free acid is selected from the dye represented by the general formula (I) and the dye represented by the general formula (II).
In the general formula (I), the group represented by A ¹ and A ² is preferably a phenyl group or a 2-naphthyl group, and more preferably each substituted with at least one —SO ₃ H group.
[0021]
The substituents represented by R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, n- Propyl group, isopropyl group, n-butyl group, trifluoromethyl group, etc.), substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.) A group selected from a —NHCOR ⁵ group (eg, —NHCONH ₂ group, —NHCOCH ₃ group, —NHCOC ₃ H ₇ (i) etc.), a halogen atom (eg, fluorine atom, chlorine atom etc.) and a —CN group Represent.
[0022]
X ¹ and X ² each independently represent a —NR ⁶ R ⁷ group or —OR ⁸ group, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted carbon number of 1 to 8 alkyl groups (for example, methyl group, carboxymethyl group, ethyl group, n-butyl group, n-octyl group, hydroxyethyl group, isopropyl group, tert-butyl group, etc.), substituted or unsubstituted carbon atoms of 1 to 3 alkenyl groups (for example, vinyl group, allyl group, etc.), substituted or unsubstituted aryl groups having 6 to 20 carbon atoms (for example, phenyl group, 4-nitrophenyl group, 4-butylphenyl group, 4-carboxyphenyl) Group), substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms (eg, benzyl group, phenethyl group, etc.), substituted or unsubstituted cyclohexyl group, or substituted or unsubstituted 5- to 6-membered nitrogen-containing Hajime Tamaki (e.g., pyridyl group) and the like. R ⁶ and R ⁷ may form a 5-membered or 6-membered ring together with the nitrogen atom to be bonded. Specifically, as —NR ⁶ R ⁷ , pyrrolidino group, piperidino group, 3,5- Examples thereof include a dimethylpiperidino group, a morpholino group, and a 4-methylpiperazinyl group.
[0023]
The dye represented by the formula (I) preferably has 2 to 8 —SO ₃ H groups as a whole molecule, and more preferably 2 to 6 —.
Of the dyes represented by the formula (I), a dye having a symmetrical structure with a linking group Y ¹ having a free acid form represented by the following formula (VIII) is preferably used. This pigment is preferable in terms of color tone, water resistance, and practicality.
[0024]
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[0025]
(In the formula, A ¹ , R ¹ , R ² , X ¹ and Y ¹ have the same meanings as the formula (I)).
In the formula (II), B ¹ and B ² each independently represent the formula (II-a) or (II-b), and in the formula (II-a), R ¹⁶ is an alkyl group having 1 to 4 carbon atoms. R ¹⁷ represents a hydrogen atom, —CN group, —CONH ₂ group, or —COOH group, and R ¹⁸ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (for example, a methyl group). For example, it represents a methyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a hydroxyethyl group, or the like.
[0026]
R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms (for example, methyl group, carboxymethyl group, ethyl group, n-butyl group, n -Alkyl groups such as octyl group, hydroxyethyl group, isopropyl group, tert-butyl group), substituted or unsubstituted alkenyl groups having 1 to 3 carbon atoms (for example, vinyl group, allyl group, etc.), substituted or unsubstituted C6-C20 aryl group (for example, phenyl group, 4-nitrophenyl group, 3-sulfophenyl group, 4-butylphenyl group, 4-carboxyphenyl group, etc.), substituted or unsubstituted C7-20 An aralkyl group (for example, benzyl group, phenethyl group, etc.), a substituted or unsubstituted cyclohexyl group, or a substituted or unsubstituted 5- to 6-membered nitrogen-containing heterocyclic group (For example, a pyridyl group etc.) etc. are mentioned.
[0027]
R ¹³ and R ¹⁴ may form a 5-membered ring or a 6-membered ring together with the nitrogen atom to be bonded. Specifically, as —NR ¹³ R ¹⁴ , a pyrrolidino group, piperidino group, 3,5-dimethylpiperidin Group, morpholino group, 4-methyl-piperazinyl group and the like.
The dye represented by the general formula (II) preferably has 2 to 8 —SO ₃ H groups as a whole molecule, more preferably 2 to 6.
[0028]
The dye used in the present invention may be used as it is in the free acid form represented by the general formula (I) or (II), but may be used as it is when it is obtained in a salt form at the time of production. And may be converted into a desired salt form. Some of the acid groups may be of a salt type, and a salt type dye and a free acid type dye may be mixed. Examples of such salt types include salts of alkali metals such as Na, Li and K, ammonium salts optionally substituted with alkyl groups and hydroxyalkyl groups, and salts of organic amines. Examples of organic amines include lower alkylamines, hydroxy-substituted lower alkylamines, carboxy-substituted lower alkylamines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.
[0029]
Further, in the structure of the dye used in the present invention, when a plurality of acid groups are contained in one molecule, the plurality of acid groups may be salt type or acid type and may be different from each other.
Specific examples of these dyes include dyes having structures shown in the following I- (1) to I- (10) and II- (1) to II- (20).
[0030]
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[0031]
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[0032]
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[0033]
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[0034]
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[0035]
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[0036]
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[0037]
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[0038]
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[0039]
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[0040]
The dye represented by the general formula (I) or (II) can be produced according to a method known per se.
For example, the dye represented by I- (1) can be produced by the steps (A) to (B). (A) From 3-amino-1,5-naphthalenedisulfonic acid (C acid) and m-toluidine, a conventional method [for example, Yutaka Hosoda, “New Dye Chemistry” (published by Gihodo on December 21, 1973) No. 396- According to page 409], a monoazo compound is produced through a diazotization coupling step.
[0041]
(B) The obtained monoazo compound is added to a cyanuric chloride suspension while maintaining pH 4 to 6 and temperature 0 to 5 ° C., and reacted for several hours. Subsequently, 1,4-bisaminopropylpiperazine, which is weakly alkaline at room temperature, is added at a 0.5 mole ratio to the monoazo compound, and a condensation reaction is performed for several hours.
[0042]
Next, a 25% aqueous sodium hydroxide solution is added to 50 to 60 ° C. to carry out a hydrolysis reaction, followed by cooling and salting out with sodium chloride to obtain the target dye.
The total content of the dye of the general formula (I) or the dye of the general formula (II) in the recording liquid is about 0.5 to 5% by weight, particularly about 2 to 4% by weight, based on the total amount of the recording liquid. Is preferred.
[0043]
As the aqueous medium used in the recording liquid of the present invention, water and a water-soluble organic solvent are used. Examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 190-400), glycerin, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethylimidazolidinone, thiodiethanol, dimethyl sulfoxide, ethylene glycol monoallyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone , Sulfolane, ethyl alcohol, isopropanol and the like are preferable. These water-soluble organic solvents are usually used in an amount of 1 to 50% by weight in the total amount of the recording liquid. On the other hand, water is used in an amount of 45 to 95% by weight based on the total amount of the recording liquid.
[0044]
The recording liquid of the present invention contains 0.1 to 10% by weight, preferably 0.5 to 5% by weight of the compound selected from urea, thiourea, biuret and semicarbazide in the total amount, or 0.001 By containing ˜5.0% by weight of a surfactant, quick drying after printing and printing quality can be further improved.
[0045]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples, unless the summary is exceeded.
[0046]
[Example 1]
Water was added to 10 parts by weight of diethylene glycol, 3 parts by weight of isopropyl alcohol, and 3 parts by weight of the dye of I- (1), and the pH was adjusted to 9 with aqueous ammonia to make the total amount 100 parts by weight.
This composition was sufficiently mixed and dissolved, pressure filtered through a Teflon filter having a pore size of 1 μm, and degassed with a vacuum pump and an ultrasonic cleaner to prepare a recording liquid.
[0047]
Using the obtained recording liquid, ink jet recording was performed on electrophotographic paper using an ink jet printer (trade name HG-3000, manufactured by Epson Corporation) to obtain a yellow print with a clear color tone. The results of various evaluations by the methods (a), (b) and (c) are shown below.
[0048]
(A) Light resistance of recorded image:
Using a xenon fade meter (product of Suga Test Instruments Co., Ltd.), the recording paper was irradiated for 100 hours, but the color fading after irradiation was small.
(B) Water resistance of recorded image:
(1) Test method After immersing the recorded image in tap water for 5 minutes,
(1) The blur of the image was examined visually.
(2) The OD value of the solid printed part before and after immersion was measured with a Macbeth densitometer (TR927).
[0049]
(2) Test results As a result of the above (1), the image was slightly blurred.
Further, the change in density of the solid print portion before and after the immersion in the above (2) was 94.2% when represented by the OD residual ratio according to the following formula.
(C) Storage stability of recording liquid:
When the recording liquid was sealed in a Teflon container and stored at 5 ° C. and 60 ° C. for 1 month, changes in the recording liquid were examined. No precipitation of insoluble matter was observed.
[0050]
[Expression 1]

[0051]
[Example 2]
Water was added to 5 parts by weight of glycerin, 10 parts by weight of ethylene glycol, and 2.5 parts by weight of the dye of II- (1), and the pH was adjusted to 9 with an aqueous lithium hydroxide solution to make the total amount 100 parts by weight. The product was processed by the method described in Example 1 to prepare a recording liquid. Using this recording liquid, printing was performed in the same manner as in Example 1. As a result, a yellow color recorded material having a clear color tone was obtained. Further, various evaluations according to (a) to (c) of Example 1 were performed on the recorded matter. As a result, similar to Example 1, good results were obtained.
Further, the residual ratio of OD was 84.5%.
[0052]
[Example 3]
Water is added to 10 parts by weight of diethylene glycol, 5 parts by weight of N-methylpyrrolidone, 3 parts by weight of isopropyl alcohol, and 3 parts by weight of the dye of II- (16), and the pH is adjusted to 9 with aqueous ammonia to make a total amount of 100 parts by weight. Then, this composition was processed by the method described in Example 1 to prepare a recording liquid. Using this recording liquid, printing was performed in the same manner as in Example 1. As a result, a yellow color recorded material having a clear color tone was obtained. Moreover, various evaluations by (a) to (c) of Example 1 were performed on the recorded matter. As a result, similar to Example 1, good results were obtained.
Further, the residual OD ratio was 86.3%.
[0053]
[Examples 4 to 27]
Instead of the dye of I- (1) used in Example 1, I- (2) to I- (10), II- (2) to II- (15), II- (17) to II -A recording liquid was prepared by the method of Example 1 except that each of the dyes of (20) was used, printing was performed, and various evaluations according to (a) to (c) of Example 1 were performed on the recorded matter. went. As a result, similar to Example 1, good results were obtained.
Further, the residual ratio of OD when using the dye of I- (2) was 86.1%, and when using the dye of I- (3), it was 80.2%.
[0054]
【The invention's effect】
The recording liquid of the present invention is used for inkjet recording and writing instruments, and when recorded on plain paper, a clear yellow-colored recorded matter can be obtained, and its print density, light resistance and water resistance are excellent. In addition, the storage stability as a recording liquid is also good.

Claims (4)

A recording liquid containing at least one dye selected from a dye represented by the following general formula (I) and a dye represented by the following general formula (II) and an aqueous medium in the form of a free acid.

[Wherein, A ¹ and A ² represent a phenyl group which may be substituted with a —SO ₃ H group or a naphthyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, —NHCOR ⁵ group (where R ⁵ is —NH ₂ or an alkyl group having 1 to 4 carbon atoms) Represents a group selected from a halogen atom and a —CN group, and X ¹ and X ² are each independently an —NR ⁶ R ⁷ group or an —OR ⁸ group (provided that R ⁶ , R ⁷ and R ⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group, and of these, other than a hydrogen atom It may have a substituent, also of R ⁶ and R ⁷ bound Together with the nitrogen atom may form a 5-6 membered ring that.) Represent,
Y ¹ represents a divalent linking group represented by any ^one of the following general formulas (III) to (VII). ]

[Wherein, B ¹ and B ² are each independently represented by the following general formula (II-a) or (II-b):

(In the general formula (II-a), R ¹⁶ represents an alkyl group having 1 to 4 carbon atoms, R ¹⁷ represents a hydrogen atom, —CN group, —CONH ₂ group, or —COOH group, and R ¹⁸ represents hydrogen. Represents an atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.)

(In the general formula (II-b), R ¹⁹ represents a hydrogen atom, a methyl group or a —COOH group, and R ²⁰ , R ²¹ and R ²² each independently represents a hydrogen atom, a —SO ₃ H group, a chlorine atom or a methyl group. R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom, —SO ₃ H group or —COOH group, and X ³ and X ⁴ each independently represent a group represented by -NR ¹³ R ¹⁴ group or -OR ¹⁵ group (where R ¹³ , R ¹⁴ and R ¹⁵ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or an aryl group. , An aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group, of which a hydrogen atom other than a hydrogen atom may have a substituent, and R ¹³ and R ¹⁴ together with the nitrogen atom to be bonded are 5-6 A member ring may be formed.)
Y ² represents a divalent linking group represented by any one of the following general formulas (III) to (VII), and n represents 0 or 1. ]

(In formula (III), a and b each represents a number of 0 to 6, and c represents 0 or 1)

(In formula (IV), V and W each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

The recording liquid according to claim 1, which is for inkjet recording. An ink jet recording method using the recording liquid according to claim 2. A dye for recording liquid in which the form of the free acid is represented by the following general formula (I) or the following general formula (II).

[Wherein, A ¹ and A ² represent a phenyl group which may be substituted with a —SO ₃ H group or a naphthyl group, and R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, A substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, —NHCOR ⁵ group (where R ⁵ is —NH ₂ or an alkyl group having 1 to 4 carbon atoms) Represents a group selected from a halogen atom and a —CN group, and X ¹ and X ² are each independently an —NR ⁶ R ⁷ group or an —OR ⁸ group (provided that R ⁶ , R ⁷ and R ⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, an aryl group, an aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group, and of these, other than a hydrogen atom It may have a substituent, also of R ⁶ and R ⁷ bound Together with the nitrogen atom may form a 5-6 membered ring that.) Represent,
Y ¹ represents a divalent linking group represented by any ^one of the following general formulas (III) to (VII). ]

[Wherein, B ¹ and B ² are each independently represented by the following general formula (II-a) or (II-b):

(In the general formula (II-a), R ¹⁶ represents an alkyl group having 1 to 4 carbon atoms, R ¹⁷ represents a hydrogen atom, —CN group, —CONH ₂ group, or —COOH group, and R ¹⁸ represents hydrogen. Represents an atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.)

(In the general formula (II-b), R ¹⁹ represents a hydrogen atom, a methyl group or a —COOH group, and R ²⁰ , R ²¹ and R ²² each independently represents a hydrogen atom, a —SO ₃ H group, a chlorine atom or a methyl group. R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom, —SO ₃ H group or —COOH group, and X ³ and X ⁴ each independently represent a group represented by -NR ¹³ R ¹⁴ group or -OR ¹⁵ group (where R ¹³ , R ¹⁴ and R ¹⁵ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or an aryl group. , An aralkyl group, a cyclohexyl group, or a nitrogen-containing heterocyclic group, of which a hydrogen atom other than a hydrogen atom may have a substituent, and R ¹³ and R ¹⁴ together with the nitrogen atom to be bonded are 5-6 A member ring may be formed.)
Y ² represents a divalent linking group represented by any one of the following general formulas (III) to (VII), and n represents 0 or 1. ]

(In formula (III), a and b each represents a number of 0 to 6, and c represents 0 or 1)

(In formula (IV), V and W each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)